WO2015015795A1 - ＳｉＯＸ粉末製造法及びＳｉＯＸ粉末製造装置 - Google Patents

ＳｉＯＸ粉末製造法及びＳｉＯＸ粉末製造装置 Download PDF

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WO2015015795A1
WO2015015795A1 PCT/JP2014/003961 JP2014003961W WO2015015795A1 WO 2015015795 A1 WO2015015795 A1 WO 2015015795A1 JP 2014003961 W JP2014003961 W JP 2014003961W WO 2015015795 A1 WO2015015795 A1 WO 2015015795A1
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sio
powder
gas
heating furnace
plasma
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PCT/JP2014/003961
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English (en)
French (fr)
Japanese (ja)
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滋 中澤
横山　和弘
朗 臼井
鈴木　義之
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東京印刷機材トレーディング株式会社
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Priority to JP2015529389A priority Critical patent/JP6352917B2/ja
Publication of WO2015015795A1 publication Critical patent/WO2015015795A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method and an apparatus for producing SiO X powder used as a negative electrode active material for a lithium ion secondary battery and a vapor deposition material for a gas barrier film.
  • a lithium ion secondary battery has a positive electrode, a negative electrode, and a separator impregnated with an electrolytic solution between the two electrodes, and is configured such that lithium ions reciprocate between the positive electrode and the negative electrode through the electrolytic solution by charging and discharging. ing.
  • an active material capable of occluding and releasing lithium ions (negative electrode active material) is used, and at present, a carbon-based negative electrode material is common.
  • the improvement in the energy density of the carbon-based negative electrode active material has reached its limit, and various negative electrode active materials have been developed with the aim of further improving the energy density.
  • Si-based negative electrode active materials are attracting attention as very promising materials.
  • the lithium ion storage capacity is about 10 times that of the carbon-based negative electrode active material.
  • Lithium ion storage capacity is lower than that of metal Si, but it is known that it is effective to use SiO as a material in which volume expansion / contraction during charge / discharge is small and charge / discharge cycle characteristics are unlikely to deteriorate.
  • SiO has different lithium ion storage capacity and volume expansion / contraction due to charge / discharge depending on the change of X value of SiO X. Accordingly, there are various means for determining the optimum point, such as the blending ratio with the carbon-based negative electrode active material and the selection of the binder. In conjunction with this, a manufacturing means capable of arbitrarily controlling the X value of SiO X is required. In general, many of the preparation of SiO X, to generate a SiO X gas in a heating furnace, it is precipitated in the precipitation substrate produce SiO X product bulk. This is pulverized and the particle diameter is adjusted to produce a negative electrode active material powder for a lithium ion secondary battery.
  • Patent Document 1 discloses a method for producing silicon monoxide.
  • silicon metal powder is introduced into a plasma jet ejected into an atmospheric gas at a supply rate of 70 g / min or more using a carrier gas.
  • the silicon metal powder not vaporized in the plasma jet is brought into contact with oxygen gas contained in at least one of the carrier gas and the atmospheric gas to cause a synthesis reaction.
  • silicon monoxide vapor is continuously generated while maintaining the reaction frame generated in the synthesis reaction.
  • the crude product obtained by quenching the generated silicon monoxide vapor is distilled at 1,400 ° C. to 1,800 ° C.
  • Patent Document 2 discloses a method for producing SiO x (X ⁇ 1) used as a negative electrode active material for a lithium ion secondary battery and a vapor deposition material for a gas barrier film.
  • a mixed raw material composed of metal Si powder and SiO 2 powder or SiO powder is vaporized by plasma heating to form SiO gas.
  • SiO X (X ⁇ 1) is vaporized by plasma heating to form SiO gas.
  • SiO X (X ⁇ 1) after depositing as silicon oxide SiO X (X ⁇ 1) on the deposition substrate, it was crushed by a ball mill to obtain powdered silicon oxide.
  • the packaging material In the field of processing food packaging, medical products, and pharmaceuticals, the packaging material is required to have high gas barrier properties so that oxygen and moisture do not permeate the packaging material in order to prevent deterioration of the food, pharmaceuticals, and the like.
  • a packaging material having a SiO vapor deposition film having high gas barrier properties and excellent transparency has been attracting attention.
  • food packaging films in which a SiO film is formed on a polymer film are produced. It should be noted that excellent transparency is necessary for observing the package contents from the appearance and confirming alteration and deterioration. In particular, it can be said to be an essential property for packaging materials for packaging foods and the like.
  • Patent Document 1 describes that a metal silicon supply rate of 70 g / min or more and a metal powder particle size of 400 ⁇ m or less (average particle size of 100 ⁇ m) are preferable.
  • silicon metal powder supplied into a plasma jet becomes vapor and reacts with oxygen gas to synthesize silicon monoxide.
  • the temperature in the reaction frame is raised to 3,000 K (2,727 ° C.) or more by heat from the plasma and reaction heat.
  • the speed of a plasma flame of a DC (direct current) plasma jet is as high as 300 m / sec or more.
  • Patent Document 1 describes that the temperature of the plasma flame is increased to 3,000 K (2,727 ° C.) or higher by heat from the plasma flame and reaction heat between the metal Si vapor and oxygen.
  • the heat of vaporization of metal Si is much larger than the heat of reaction, and when the amount of material supply increases, the temperature of the plasma flame rapidly decreases, and there is a problem that a large amount of metal Si that cannot be vaporized remains.
  • the material supply amount and the theoretical oxygen amount were calculated and introduced at the target stoichiometric atomic weight ratio, the temperature was not uniform in the plasma flame and the temperature difference was partially large, so it was introduced and scattered. A uniform oxidation reaction with metal Si does not occur. Therefore, the oxidation reaction proceeds partially, and the ratio of vaporized metal Si to SiO 2 becomes very large.
  • Patent Document 2 a mixed raw material composed of metal Si powder and SiO 2 powder or SiO powder is vaporized by plasma heating to form SiO gas, and then deposited on a deposition substrate as silicon oxide SiO X (X ⁇ 1). It is described.
  • the center temperature of the plasma flame is preferably 5,000 ° C. to 100,000 ° C., more preferably only 10,000 ° C. to 20,000 ° C.
  • Patent Document 2 does not describe what plasma operation conditions, raw material particle diameters, and material supply speeds are used in which plasma apparatus. For example, when an RF (high frequency induction) thermal plasma apparatus is used, the heat capacity of the plasma flame is very small even if the temperature of the plasma flame is an ultrahigh temperature of 10,000 ° C. or higher. Accordingly, some metal Si having a small particle size melt and vaporize, but a large number of ones having a large particle size are spheroidized and solidified as they are, and it is difficult to produce SiO.
  • RF high frequency induction
  • the plasma flame is a very hot gas but has a very small heat capacity, while the heat of vaporization of metal Si is very large. Is because it does not vaporize.
  • the mixed raw material consisting of the metal Si powder and the SiO 2 powder or the SiO powder charged into the plasma flame is scattered in all directions and the vaporization temperature is greatly different, so the mixed particles of the metal Si powder and the SiO 2 powder This is because the synthesis reaction is difficult to occur. That is, a mixed powder of metal Si powder and SiO 2 powder and / or SiO powder is put into a plasma flame at 10,000 ° C. to 20,000 ° C., and all these are completely vaporized to cause SiO X conversion reaction.
  • Patent Document 2 it is insufficient to completely evaporate the mixed powder of the metal Si powder and the SiO 2 powder and / or the SiO powder to cause the SiO X conversion reaction.
  • Patent Document 2 in order to suppress splash, when a raw material that generates SiO gas is heated to a high temperature by a plasma flame, vaporized metallic silicon and oxygen react in an atomic state to generate SiO gas, and this SiO gas It is said that SiO X (X ⁇ 1) obtained by precipitating is effectively distributed uniformly without containing crystalline metallic silicon and silicon dioxide and becomes amorphous. Splash is a phenomenon in which fine particles of metal silicon and silicon dioxide that are not vaporized are scattered together with vaporized SiO gas. If splash is generated when forming the SiO vapor deposition film, fine particles that are not vaporized adhere to the SiO vapor deposition film on the polymer film, causing defects such as pinholes, and gas barrier properties are deteriorated.
  • the metal Si powder and the SiO 2 powder are not vaporized in the plasma flame and become an atomic state, but in most cases, they are not vaporized but remain as droplets. is there. That is, it is important in what kind of particle size powder raw material is heated in which plasma flame (temperature, plasma flame speed) of the plasma apparatus, but this is described in Patent Document 2. Absent. In the case of a temperature of 10,000 ° C. plasma flame of a DC (direct current) plasma spray gun, the average particle size D 50 generally used in the DC (direct current) plasma spray gun is 30 ⁇ m because the speed of the plasma flame is high. Even if a level of metal Si powder is supplied, most of the powder is only partially melted and hardly gasified.
  • the present invention has been made in order to solve the above-described problems, and its purpose is to continuously and inexpensively produce SiO X powder used as a negative electrode active material of a lithium ion secondary battery and a vapor deposition material of a gas barrier film. and to provide a SiO X powder preparation and SiO X powder production apparatus capable of.
  • the SiO X powder production method of the present invention includes a step of heating and melting a mixed granulated powder of metal Si powder and SiO 2 powder with a plasma flame, and vaporizing molten droplets of the heated and melted mixed granulated powder in a heating furnace. And a step of causing the SiO X reaction to be performed, and a step of rapidly cooling the generated SiO X gas with an inert gas to precipitate SiO X fine powder.
  • the SiO X powder production apparatus of the present invention is a mixed granulation of a DC (direct current) plasma apparatus or an RF (high frequency induction) thermal plasma apparatus equipped with a plasma gun for ejecting a plasma flame, and a metal Si powder and SiO 2 powder.
  • Powder supply device for spraying powder into plasma flame, heating furnace for vaporizing molten droplets of mixed granulated powder heated and melted in plasma flame to perform SiO X conversion reaction, and generated SiO X gas
  • a cooling device for precipitating SiO X fine powder by rapid cooling with an inert gas.
  • high purity (4N or more) Si powder is used as a metal Si powder raw material.
  • the high-purity (4N or higher) Si powder is used by regenerating metal Si sludge generated in a silicon wafer manufacturing process such as for semiconductors and solar cells to a high purity (4N or higher).
  • metal Si used for semiconductors, solar cells and the like has been purified to a very high purity.
  • the powder generated in the silicon wafer slicing and polishing process is very difficult to handle with fine particles, collected as sludge contaminated with impurities, and processed as waste as cost.
  • the present invention is a metal Si powder and SiO 2 powder, each having an average particle diameter D 50 of 10 ⁇ m or less, preferably have an average particle diameter D 50 using the following metal Si powder and SiO 2 powder 5 [mu] m, SiO X
  • the mixing ratio of the metal Si powder and the SiO 2 powder is set so that the X value of is 0.5 to 1.8.
  • the present invention water in these mixed powder materials, solvent, dispersing agent, by mixing a binder, well stirred mixture by a mixer, spray drying method obtained by slurrying the average particle diameter D 50 at (spray-dried) It is preferable to use a mixed granulated powder of metal Si powder and SiO 2 powder granulated to 10 ⁇ m to 50 ⁇ m.
  • the metal Si powder and the SiO 2 powder are uniformly mixed and granulated at a constant ratio, and the raw material is used as a secondary raw material.
  • This secondary raw material which is a mixed granulation of metal Si powder and SiO 2 powder, enhances the reactivity between fine powders, and melts the mixed granulated powder of metal Si powder and SiO 2 powder in the plasma flame. It has a great effect on vaporization.
  • the metal Si powder and the SiO 2 powder are present in a certain ratio in the particles of the mixed granulated powder of the metal Si powder and the SiO 2 powder, the X value of the SiO X gas has an extremely stable atomic ratio. Easy to composition.
  • the present invention uses a DC (direct current) plasma device or an RF (radio frequency induction) thermal plasma device as a device for generating a plasma flame, and a metal Si powder and SiO for a plasma flame of 6,000 K (5,727 ° C.) or more.
  • the mixed granulated powder with 2 powders is blown and melted by heating (partially vaporized).
  • a DC (direct current) plasma apparatus is characterized by a high speed flame that is a plasma flame.
  • a DC (direct current) plasma device is a high-adhesion coating film that is made by introducing a high melting point ceramic powder into a Mach 2 level plasma jet such as plasma spraying, instantly melting the material and welding it to the substrate at high speed. Is generally used to form
  • the DC (direct current) plasma apparatus uses the mixed granulated powder of the metal Si powder and the SiO 2 powder as a raw material and heats and melts (partially vaporizes) the mixed granulated powder as in the present invention.
  • the frame speed is too fast.
  • a material having a large heat of fusion and heat of vaporization, such as metal Si is insufficient in terms of heat amount and reaction time for vaporization even if it is melted. Therefore, the DC (direct current) plasma device increases the nozzle diameter at the tip of the plasma gun and makes the material flight speed in the plasma flame 150 m / sec or less, thereby increasing the reaction time and melting and vaporizing. And a special structure that promotes chemical reactions.
  • a heating furnace is installed in front of the plasma gun in order to completely gasify the metal Si that is not vaporized and the SiO 2 powder to cause a synthetic reaction.
  • a graphite heater heating furnace or a high-frequency induction heating furnace is used as the heating furnace, a highly heat-resistant graphite pipe is used as the reaction tube, the periphery of the graphite tube is insulated, and further water-cooled.
  • the droplet melted by the plasma flame is further heated and vaporized while maintaining the temperature in the graphite tube at 2,000 K (1,727 ° C.) or higher, thereby completely generating SiO X gas. That is, all of the droplets melted by the plasma flame are gasified, so that the generated SiO X has a uniform composition.
  • SiO X as SiO X also gas barrier film for vapor deposition material as a negative electrode active material of a lithium ion secondary battery, when without vaporizing unreacted metal Si and SiO 2 remains, deterioration in charge-discharge characteristics of the negative electrode And lead to deterioration of gas barrier properties.
  • a compressed inert gas such as N 2 or Ar is jetted and mixed from the ring-shaped nozzle at the outlet of the heating furnace, and the high-temperature SiO X gas is rapidly cooled to 800 ° C. or less to 0.01 ⁇ m
  • a cooling device for precipitating ⁇ 10 ⁇ m SiO X fine powder is provided.
  • High-temperature SiO X gas of 2,000 K (1,727 ° C.) or more generated in the reaction tube of the heating furnace is N 2 , Ar, or the like ejected from the ring-shaped nozzle of the cooling device provided at the outlet of the heating furnace. by being suddenly cooled to 800 ° C.
  • the inside of the heating furnace is preferably operated under a reduced pressure of 30 kPa to 80 kPa.
  • a reduced pressure of 30 kPa to 80 kPa By operating the inside of the reaction tube of the heating furnace under a reduced pressure of 30 kPa to 80 kPa, the reaction temperature between the metal Si powder and the SiO 2 powder can be lowered and the SiO conversion reaction can be further promoted.
  • This decompression operation is not an absolute requirement, and the decompression facility may be appropriately determined based on the investment and its effect.
  • the degree of pressure reduction of 30 kPa to 80 kPa is not particularly limited, and is optimal depending on various operating conditions such as the particle diameter of the feed material (granulated powder), the supply amount, the output of the plasma apparatus, the temperature of the heating furnace, etc.
  • the precipitated SiO X fine powder of 0.01 ⁇ m to 10 ⁇ m is cooled with a water-cooled cyclone so that the average particle diameter D 50 grows or aggregates into a fine powder of 1 ⁇ m to 20 ⁇ m and is collected.
  • the SiO X powder produced by cooling with a compressed inert gas such as N 2 and Ar has a particle size that is too fine and poor in recovery efficiency.
  • the recovery rate of the SiO X powder is obtained by growing the particle diameter in a water-cooled cyclone. There is an effect to raise.
  • the water-cooled cyclone has an outer periphery that is water-cooled, and is blown by a high-flow rate of compressed inert gas such as SiO X fine powder and N 2 , Ar that has been primarily cooled to 800 ° C. or less.
  • the resulting SiO X fine powder is cooled to 200 ° C. or lower to grow or aggregate the particle diameter. It is preferred to recover most of the SiO X fine powder in a water-cooled cyclone.
  • the average particle diameter D 50 of the recovered SiO X fine powder by a 1 [mu] m ⁇ 20 [mu] m, when used as the negative electrode active material of a lithium ion secondary battery, it is not necessary to pass the milling step or the like, significant cost reduction effective.
  • the present invention it is preferable to collect uncollected ultra fine powder by a bag filter using a water cooling cyclone.
  • SiO X fine particles of submicron (1 ⁇ m or less) or less cannot be completely recovered. Therefore, these fine particles are completely removed by a bag filter, and the exhaust gas is discharged into the atmosphere in a clean state.
  • the present invention is to cool N 2 and Ar gas, which are clean exhaust gas after dust collected by a bag filter, with a water-cooled cyclone, to a room temperature with a heat exchanger, and further with a high-pressure blower. Pressurize and circulate through an inert gas cooler.
  • average particle diameter D 50 means a particle diameter at an integrated value of 50% in a particle diameter distribution determined by a laser diffraction / scattering method.
  • a SiO X- based active material having a large lithium ion storage capacity, a small volume expansion / contraction shrinkage of the active material coating film due to charge / discharge, and excellent charge / discharge cycle characteristics can be controlled arbitrarily.
  • it can be continuously produced at a low cost with an optimum particle size without going through a pulverization step.
  • metal Si sludge generated in a silicon wafer manufacturing process for semiconductors, solar cells, etc. is regenerated to high purity (4N or more) and is therefore excellent in environmental measures. .
  • this waste sludge can be regenerated for high purity at low cost, there is an advantage that raw material costs can be kept low.
  • this waste sludge has already had an optimal particle size distribution suitable for the purpose of granulation as a granulated powder that is a raw material used in the plasma apparatus, and the pulverization process for pulverization can be omitted. This greatly reduces costs.
  • the molten droplets of the mixed granulated powder heated and melted (partially vaporized) by the plasma flame are vaporized in the heating furnace to cause the SiO X conversion reaction, thereby generating the SiO X gas. All are gasified, and the resulting SiO X has a uniform composition. For this reason, unreacted metal Si remains, so that it is possible to solve the conventional problem that the charge / discharge characteristics and gas barrier characteristics of the lithium ion secondary battery are deteriorated, and the recovery yield of SiO X is increased. .
  • the metal Si powder and the SiO 2 powder are granulated to obtain a mixed granulated powder having an average particle diameter D 50 of 10 ⁇ m to 50 ⁇ m.
  • the material can be supplied stably with the supply device. Therefore, as in the conventional powder supply device, the smaller the particle diameter, the more unstable the supply amount, and it is difficult to produce a stable and uniform mixing ratio, and there is a special material supply device. The problem of being necessary can be solved.
  • a high temperature SiO X gas of 2,000 K (1,727 ° C.) or higher generated in a heating furnace is provided with a cooling device at the outlet of the heating furnace, and is compressed inactive such as N 2 and Ar. gas ejected mixture from the ring-shaped nozzle, rapidly cooled to 800 ° C. or less, since the precipitating SiO X fine powder can remain composition SiO X, to deposit the amorphous SiO X microparticles.
  • N 2 for the compressed inert gas because the cooling efficiency is good and the cost is low.
  • the inside of the heating furnace is operated under a reduced pressure of 30 kPa to 80 kPa, it is possible to lower the vaporization temperature of the mixed molten droplets of the metal Si powder and the SiO 2 powder and further promote the SiO X conversion reaction. it can.
  • SiO X fine powder 200 since blowing SiO X powder and N 2, compressed inert gas such as Ar that has been primary cooling to 800 ° C. or less at a high flow rate circumferentially of water cooling cyclone, SiO X fine powder 200 Since the particle diameter grows or aggregates when cooled to below °C, most of the SiO X fine powder can be recovered in a water-cooled cyclone. Further, the average particle diameter D 50 of the recovered SiO X fine powder can be set to 1 ⁇ m to 20 ⁇ m.
  • the average particle diameter D 50 of the recovered SiO X fine powder is 1 ⁇ m to 20 ⁇ m, it is necessary to go through a fine pulverization step or the like when used as a negative electrode active material of a lithium ion secondary battery. There is no significant cost reduction effect.
  • submicron (1 ⁇ m or less) SiO X fine particles that cannot be completely recovered by a water-cooled cyclone can be completely removed by a bag filter, and the exhaust gas can be discharged into the atmosphere in a clean state.
  • clean exhaust gas after collecting and collecting SiO X particulates with a bag filter is cooled to room temperature with a heat exchanger, then boosted with a high-pressure blower, and recycled to the cooling device. Cost reduction is possible.
  • the working gas N 2 , Ar gas, etc.
  • the extent to which the inert gas is circulated and used can be determined by the equipment cost and the running cost for the exhaust gas after the bag filter is clean.
  • the cross-sectional structure of the SiO X powder production apparatus used in the first embodiment of the SiO X powder production method according to the present invention is a diagram schematically showing. It is a schematic diagram which shows the cross-sectional structure of the DC plasma gun front-end
  • the cross-sectional structure of the SiO X powder production apparatus used in the second embodiment of the SiO X powder production method according to the present invention is a diagram schematically showing. It is a diagram showing a sectional structure of a cooling device for cooling by compressed N 2 gas in FIG.
  • the SiO X powder manufacturing method of the present embodiment will be described based on the steps (A) to (E).
  • the DC (direct current) plasma apparatus 1 is operated to supply the mixed granulated powder 5 of the metal Si powder and the SiO 2 powder from the powder supply nozzle 4 to the plasma flame 3 ejected from the plasma gun 2.
  • the mixed granulated powder 5 is heated and melted (partially vaporized).
  • the mixed granulated powder 5 is granulated by mixing the metal Si powder and the SiO 2 powder in the powder granulator 13, and then the powder supply disposed near the plasma gun tip 2 a via the powder feeder 14. It is supplied from the nozzle 4 to the plasma flame 3.
  • the molten droplets of the mixed granulated powder 5 that has been heated and melted (partially vaporized) in the step (A) are placed in the graphite tube (reaction tube) 15 of the high-frequency induction heating furnace 19. It is vaporized at a high temperature to cause the SiO X conversion reaction.
  • the SiO X gas generated in the step (B) is rapidly cooled using a compressed inert gas such as N 2 or Ar in the gas cooling device 20 to precipitate the SiO X fine powder 25a.
  • the SiO X fine powder 25a deposited in the step (C) is cooled by the water-cooled cyclone 24 and recovered as a fine powdery SiO X powder 25b grown or aggregated.
  • uncollected ultrafine powder is collected by the bag filter 27 by the water cooling cyclone 24 and collected.
  • a SiO X fine powder used as a vapor deposition material of the negative electrode active material and the gas barrier film of the lithium ion secondary battery it is possible to obtain a SiO X fine powder used as a vapor deposition material of the negative electrode active material and the gas barrier film of the lithium ion secondary battery.
  • the SiO X powder manufacturing apparatus of the present embodiment includes a DC (direct current) plasma apparatus 1 including a plasma gun 2 that ejects a plasma flame 3.
  • a powder supply nozzle 4 for spraying a mixed granulated powder 5 of a metal Si powder and a SiO 2 powder in a plasma flame 3 ejected from a DC (direct current) plasma apparatus 1 is arranged in the vicinity of the plasma gun tip 2a. .
  • the molten droplets of the mixed granulated powder 5 that is heated and melted (partially vaporized) by the plasma flame 3 ejected from the DC (direct current) plasma apparatus 1 are vaporized.
  • a high frequency induction heating furnace 19 for performing the SiO x conversion reaction is disposed.
  • a cooling device 20 is disposed that rapidly cools the SiO x gas generated in the high-frequency induction heating furnace 19 with an inert gas to precipitate the SiO x fine powder 25a.
  • a water-cooled cyclone 24 that cools the SiO X fine powder 25 a deposited by the cooling device 20 and collects it as a fine powdery SiO X powder 25 b grown or aggregated is disposed.
  • a bag filter 27 for collecting and collecting uncollected SiO x fine powder by the water-cooled cyclone 24 is disposed.
  • the metal Si sludge generated in the semiconductor or solar cell silicon wafer manufacturing process is regenerated into the metal Si powder used in the mixed granulated powder 5 of the metal Si powder and the SiO 2 powder in the step (A). And use it.
  • the powder particle diameter, impurity content, moisture content, and the like vary depending on the location where the metal Si sludge is generated, it is pretreated according to its properties and refined into metal Si powder.
  • purification methods such as impurity removal, dehydration, pulverization of agglomerated powder, and drying, and the method is not particularly limited.
  • the metal Si powder and the SiO 2 powder those having an average particle diameter D 50 of 10 ⁇ m or less, more preferably, an average particle diameter D 50 of 5 ⁇ m or less are used.
  • each average particle diameter D 50 exceeds 10 ⁇ m, the variation in the mixing ratio of the metal Si powder and the SiO 2 powder in one particle when granulated increases. Further, the surface area of the contact interface between the metal Si powder and the SiO 2 particles when blown into the plasma flame 3 to form a molten droplet is reduced, and the effect of increasing the reactivity between the metal Si and SiO 2 is less likely to occur.
  • the lower limit of the average particle diameter D 50 of the SiO 2 powder is not particularly limited.
  • the metal Si powder may natural oxide film on the outermost surface
  • the average particle diameter D 50 is fine particles of less than 1 [mu] m, high reactivity, it is difficult to handle. Therefore, the lower limit of the average particle diameter D 50 of the metal Si powder and 1 [mu] m.
  • the mixing ratio of the metal Si powder and the SiO 2 powder is adjusted so that the X value of the target SiO X powder is 0.5 to 1.8.
  • the lithium ion storage capacity and charge / discharge cycle characteristics due to volume expansion / contraction due to charge / discharge of the SiO X coating film are inversely proportional to the magnitude of the X value. It is necessary to select an optimum value among X values of 0.5 to 1.8. When the X value is less than 0.5, the lithium ion storage capacity increases, but the charge / discharge cycle characteristics due to the expansion and contraction of the active material film deteriorate, which is not practical. When the X value exceeds 1.8, the expansion and contraction of the active material film has almost no problem, but an increase in the lithium ion storage capacity cannot be expected so much.
  • silica and alumina are compared as a gas barrier material, silica has better gas barrier properties and flexibility, but has the disadvantage of being yellowish, and alumina is colorless and transparent and cheap, but hard and brittle. There is a disadvantage that the gas barrier property is inferior.
  • the silica deposited film is used in an oxidized state where the X value of SiO X is about 1.5 to 1.8. When the X value approaches 1.0, the gas barrier property is increased, but it becomes yellowish. On the contrary, when the X value approaches 2.0, there is a problem that the color tone becomes thin but the gas barrier property is lowered, and the control of the degree of oxidation becomes important.
  • the X value can be selected depending on the use of the film depending on whether the gas barrier property is taken or the transparency of the film is taken.
  • the important thing is that it does not contain metallic Si, the X value in the case of gas barrier material is 1.5 to 1.8, and the X value in the case of the negative electrode active material of lithium ion secondary battery is about 0.5 to 1.8. It is to build stably to the target value.
  • the average particle diameter D 50 of the mixed granulated powder 5 of metal Si powder and SiO 2 powder is preferably 10 ⁇ m to 50 ⁇ m, and the average particle diameter D 50 is more preferably 15 ⁇ m to 40 ⁇ m. This is because when the average particle diameter D 50 is less than 10 ⁇ m, the supply amount of the powder supply device 14 to the plasma gun 2 varies greatly, and stable production of SiO X cannot be performed.
  • the granulation method of the metal Si powder and the SiO 2 powder is not particularly limited, such as a spray drying method, a tumbling granulation method, a fluidized granulation method, a stirring granulation method, etc.
  • a spray drying method is preferred.
  • fine particles (primary particles) of up to several ⁇ m and a liquid organic binder are mixed in a mixing tank, slurried, then fed into a chamber by a pump and sprayed with compressed air. This is dried as agglomerated particles (secondary particles) from above by a dry air stream and collected by the lower collector.
  • the organic binder polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), starch, paraffin, resin or the like is used.
  • step (A) a DC (direct current) plasma apparatus 1 was used as the plasma heating apparatus.
  • the plasma gun tip 2 a is an electrode in which the cathode 7 is disposed in the working gas passage 8 and the working gas (N 2 or the like) 9 is ejected from the working gas passage 8 along the cathode 7.
  • a holder 6 and a nozzle 10 composed of an anode communicating with the electrode holder 6 are provided.
  • a water jacket 11 that is cooled by cooling water 12 is provided on the outer periphery of the nozzle 10.
  • a working gas (N 2 or the like) 9 ejected from the electrode holder 6 is ejected from the plasma gun tip 2a as a plasma flame 3 by discharge between the cathode 7 and the anode. Further, the plasma gun tip 2a increases the diameter of the nozzle 10 in order to slow down the ejection speed of the plasma flame 3, so that the speed of the plasma flame 3 is 150 m / sec or less, and the reaction time is increased to increase the metal Si powder.
  • This is a special structure that promotes the melting and vaporization of the mixed granulated powder 5 of SiO 2 and SiO 2 powder.
  • a mixed granulated powder 5 of metal Si powder and SiO 2 powder is supplied by a carrier gas (N 2 or the like) toward a plasma flame 3 ejected from the plasma gun 2
  • a powder supply nozzle 4 of a supply system is arranged.
  • the powder supply nozzle 4 has an internal supply system and an external supply system (not shown). From the viewpoint of efficiently supplying the material to the high temperature part of the plasma flame 3 and increasing the melting efficiency of the material, the internal supply method is preferable. However, in the internal supply method, the anode constituting the nozzle 10 is easily damaged.
  • the powder supply location is preferably from 1 to 4 locations in the circumferential direction of the nozzle 10 toward the center of the plasma flame 3.
  • a powder supply device 14 for supplying a mixed granulated powder 5 of a metal Si powder and a SiO 2 powder granulated by the powder granulator 13 is connected to the powder supply nozzle 4 via a pipe.
  • the DC (direct current) plasma device 1 is used as the plasma device for realizing the step (A).
  • the present invention is not limited to the DC (direct current) plasma device 1, but RF (high frequency induction).
  • a thermal plasma apparatus or the like may be used.
  • the DC (direct current) plasma apparatus 1 is preferable in order to have high thermal energy conversion efficiency, to completely vaporize the metal Si powder, and to efficiently process the SiO X conversion reaction in a large amount.
  • the DC (direct current) plasma apparatus 1 can melt the mixed granulated powder 5 of metal Si powder and SiO 2 powder at a high temperature of 6,000 K (5,727 ° C.) or more with the plasma flame 3.
  • SiO X can be combined with the step (B) of completely vaporizing the high temperature induction furnace 19 at a high temperature of 2,000 K (1,727 ° C.) or higher.
  • a normal DC (direct current) plasma apparatus is characterized in that the velocity of the flame, which is the plasma flame 3 of the plasma jet, is obtained at a high flow rate of Mach 2 level.
  • the speed of the frame at the outlet of the plasm gun tip 2a is made as low as possible. Therefore, the diameter of the nozzle 10 of the plasma gun tip 2a is increased so as to slow down the flying speed of the raw material powder, and the flying speed of the SiO X droplet is set to 150 m / sec to 3 m / sec. 19 is blown into the structure.
  • the diameter of the nozzle 10 of the plasma gun tip 2a is configured to expand stepwise or in a curve toward the tip of the nozzle 10 in order to adjust the flying speed of the SiO X droplet, and the anode and cathode 7 is a structure that can be exchanged as a pair of parts combined with a structure that maintains the distance to 7 appropriately.
  • the flying speed of the SiO X droplet exceeds 150 m / sec, the reaction time in the high-frequency induction heating furnace 19 is short, and it is difficult to cause the reaction to be completely vaporized in the high-frequency induction heating furnace 19.
  • the flying speed of the SiO X droplet is less than 3 m / sec, a coarse droplet that cannot be vaporized does not fly to the optimum reaction temperature portion in the high-frequency induction heating furnace 19 and may accumulate on the bottom of the high-frequency induction heating furnace 19. is there.
  • an RF (high frequency induction) thermal plasma apparatus can produce a high-temperature plasma flame of 10,000 K (9,727 ° C.) or higher, but has a low thermal energy conversion efficiency to plasma, and a feed rate of 10 g / min. Therefore, the productivity is poor and the production cost is high, which is not preferable as a mass production apparatus.
  • a high frequency induction heating furnace 19 is connected to the tip of the DC (direct current) plasma apparatus 1 in order to realize the step (B).
  • a graphite tube (reaction tube) 15 having a heat-resistant temperature of 3,000 ° C., which is covered with a heat insulating material 16, is inserted into the water-cooled quartz tube 17, and the high-frequency induction furnace is disposed around the water-cooled quartz tube 17.
  • the coil 18 is arranged.
  • the internal temperature of the graphite tube (reaction tube) 15 can be arbitrarily controlled from 1,600 ° C. to 2,700 ° C.
  • the opening 15a provided in the upper part of the graphite tube (reaction tube) 15 is cooled by cooling with a compressed inert gas such as N 2 or Ar in order to realize the step (C).
  • a device 20 is arranged.
  • the high-frequency induction heating furnace 19 for realizing the step (B) has a temperature in the graphite tube (reaction tube) 15 of 2,000 K (1,727 ° C.) or higher so that the SiO X conversion reaction is sufficiently performed. It is preferable to use a graphite tube having a high heat resistance temperature.
  • a method of producing SiO X by blowing metal Si powder into a DC (direct current) plasma jet and using oxygen gas O 2 as a working gas is also conceivable.
  • a cooling device 20 that performs cooling with a compressed inert gas such as N 2 or Ar is connected to an opening 15 a provided at an upper portion of a graphite tube (reaction tube) 15, and has a normal temperature.
  • the ring-shaped nozzle 22 is connected to a pipe line 22a that communicates with a device (not shown) that supplies a compressed inert gas such as N 2 or Ar at room temperature.
  • the heat insulation double pipe 23 is provided with an inlet 23a for taking in cooling water or a compressed inert gas such as N 2 and Ar, and an outlet 23b.
  • the high temperature SiO X gas of 2,000 K (1,727 ° C.) or more generated in the graphite tube (reaction tube) 15 of the high frequency induction heating furnace 19 is the upper part of the graphite tube (reaction tube) 15 of the high frequency induction heating furnace 19. It is introduced into the cooling device 20 that is connected to the opening 15a.
  • a compressed inert gas such as N 2 or Ar is jetted in an oblique direction from a ring-like nozzle 22 that jets in a ring shape, and high-temperature SiO X gas is sucked by the ejector effect and instantly cooled to 800 ° C. or less, Amorphous SiO X fine powder 25a is deposited. This SiO X gas becomes an almost stable solid at 800 ° C. or lower.
  • the SiO X precipitate is deposited as submicron (1 ⁇ m or less) amorphous SiO X fine powder 25a without being disproportionated into the metal Si powder and the SiO 2 powder. Since the particle diameter of the SiO X fine powder 25a is very fine with a submicron (1 ⁇ m or less), it is difficult to collect with a normal cyclone. Therefore, by blowing compressed inert gas such as N 2 or Ar for primary cooling, the gas flow rate in the heat insulating double pipe 23 is increased, and the water is cooled primarily to 800 ° C. or less in the circumferential direction in the water cooling cyclone 24. Introduced high temperature gas.
  • compressed inert gas such as N 2 or Ar
  • the heat insulating double pipe 23 serving as a guide pipe to the water cooling cyclone 24
  • the heat insulating double pipe 23 is N 2 , Ar for cooling water or primary cooling.
  • cooling is performed through a compressed inert gas such as the like, and the inert gas is blown from the ring-shaped nozzle 22.
  • the heat insulation double tube 23 is cooled with water or a cooling gas. However, if it is cooled too much, SiO X gas is deposited as a SiO X solid and deposited in the heat insulation double tube 23, and the heat insulation double tube 23 is clogged. End up. In order to collect the SiO X solid (powder or flakes) deposited and deposited in the heat insulating double tube 23, the operation must be a batch operation in a short cycle. Therefore, when the heat insulation double pipe 23 is indirectly cooled with water, it is necessary to adjust the flow rate and the like so as to maintain a temperature at which the SiO X gas does not precipitate in the heat insulation double pipe 23.
  • the insulated double pipe 23 temperature can be maintained at a high temperature. Moreover, since the gas flow rate in the pipe is very fast, problems such as deposit clogging do not occur.
  • process (D) is demonstrated.
  • the heat insulating double tube 23 of the cooling device 20 that performs cooling with a compressed inert gas such as N 2 or Ar communicates with the water cooling cyclone 24.
  • the SiO X fine powder 25a cooled here grows or aggregates as the particle size grows and agglomerates and deposits on the side walls and the lower part of the cyclone.
  • a hopper 26 that recovers the SiO X powder 25b that has been cooled by the water-cooled cyclone 24 and whose particle diameter has grown or aggregated and deposited and deposited on the side wall and the lower part of the cyclone.
  • the cooling efficiency is very good, and the fine powder SiO X powder 25b is further rapidly cooled, so that the particle size becomes a secondary particle. greatly grow or aggregate as an average particle diameter D 50 is the powder of 10 [mu] m ⁇ 20 [mu] m.
  • D 50 is the powder of 10 [mu] m ⁇ 20 [mu] m.
  • the SiO X gas when the SiO X gas is rapidly cooled with a compressed inert gas such as N 2 or Ar, the size of the precipitation growth nuclei varies depending on the cooling rate, but generally becomes a fine powder of 0.01 ⁇ m to several ⁇ m, and the amorphous non-crystalline It can be a crystal structure.
  • SiO usually has a metastable crystal structure and has an amorphous aggregate structure of metal Si and SiO 2 , but when heated in a high temperature region of 800 ° C. or higher, it gradually becomes dissociated by the disproportionation reaction. Separated into SiO 2 region.
  • the particle diameter is preferably adjusted to 0.01 ⁇ m to 10 ⁇ m by adjusting the amount of compressed inert gas such as N 2 or Ar.
  • Nanoparticles with a particle size of SiO X fine powder of less than 0.01 ⁇ m have a large particle surface area and are difficult to knead with a binder when used as a negative electrode active material for a lithium ion secondary battery. Problems are likely to occur.
  • particles having a particle size of SiO X fine powder exceeding 10 ⁇ m are liable to crack or peel off from the electrode due to volume expansion / contraction due to absorption / release of lithium ions, and as a negative electrode active material for lithium ion secondary batteries. Is not preferred.
  • process (E) is demonstrated.
  • the water-cooled cyclone 24 communicates with a bag filter 27 that sucks and collects the SiO X fine powder not deposited here by a vacuum pump 28 via a pipe line 24a.
  • the submicron (1 ⁇ m or less) SiO X fine powder that could not be collected in the water-cooled cyclone 24 is removed by the bag filter 27 in step (E), and clean exhaust gas is released to the atmosphere.
  • the dust collected here is also collected as a SiO X powder product, the product yield is also increased.
  • the inside of the high-frequency induction heating furnace 19 is operated under a reduced pressure of 30 kPa to 80 kPa, thereby lowering the reaction temperature between the metal Si powder and the SiO 2 powder and further promoting the SiO X conversion reaction. Can do.
  • all the processes from the high-frequency induction heating furnace 19 to the bag filter 27 are operated under reduced pressure by suctioning with the vacuum pump 28 behind the bag filter 27.
  • the vaporization temperature of SiO X is lowered, so that the temperature in the high-frequency induction heating furnace 19 can be kept low, and the heating capacity of the high-frequency induction coil 18 can also be reduced.
  • the cooling device 20 introduces an initially charged compressed inert gas into a pipeline 22 a connected to the ring-shaped nozzle 22 via a three-way valve 22 b and a circulating compressed inert gas.
  • the pipe line 22d to be connected is connected.
  • the inert gas circulation device includes a bag filter 27 and an inert gas cooling device 34.
  • the bag filter 27 is provided with a conduit 29 that guides clean exhaust gas that has passed through the bag filter 27.
  • the bag filter 27 communicates with the water cooling cyclone 24 via a pipe line 24a.
  • the inert gas cooling device 34 is provided on the downstream side of the pipe line 29, the heat exchanger 30 for cooling the exhaust gas to room temperature, the pipe line 31 provided on the downstream side of the heat exchanger 30, and the pipe line
  • the high pressure blower 32 is provided downstream of the high pressure blower 31 and boosts the exhaust gas.
  • the high pressure blower 32 is connected to the downstream side of the high pressure blower 32 and the pipe 22 d of the cooling device 20.
  • the pipe 33 is provided with an exhaust pipe 35 through a three-way valve 36 that discharges surplus gas equivalent to the working gas (N 2 , Ar gas, etc.) blown by the plasma gun 2 to the atmosphere.
  • Example 1 As a primary raw material of metal Si powder, metal Si powder regenerated from metal Si sludge generated in a silicon wafer production process for semiconductor production was used. The purity of the metal Si powder was impurity heavy metal ⁇ 50 ⁇ g / g, average particle diameter D 50 : 3.7 ⁇ m. The particle size distribution of the SiO 2 powder was an average particle size D 50 : 2.4 ⁇ m. A powder obtained by mixing metal Si powder and SiO 2 at a weight ratio (wt%) of 1: 2.14 (X value of SiO X : 1.0), water, an organic binder (PVA), and a dispersant.
  • wt% weight ratio
  • the average particle diameter D 50 of the mixed granulated powder 5 was 17 ⁇ m ( ⁇ 60 ⁇ m).
  • a DC (direct current) plasma apparatus manufactured by Nippon Yutech Co., Ltd .: SG-100 spray gun 1 was used as the plasma heating apparatus.
  • a special nozzle in which the diameter of the nozzle 10 at the plasma gun tip 2a is increased in order to slow down the ejection speed of the plasma flame 3.
  • a mixed granulated powder 5 of metal Si powder and SiO 2 powder was supplied to a DC (direct current) plasma apparatus 1 by a carrier gas (N 2 ) at a supply rate of 30 g / min.
  • N 2 60 L / min
  • a high frequency induction heating furnace 19 was connected to the tip of the DC (direct current) plasma apparatus 1.
  • the high frequency induction heating furnace 19 has a structure in which a heat insulating material 16 and a graphite tube (reaction tube) 15 having a heat resistant temperature of 3,000 ° C. are inserted into a water-cooled quartz tube 17 and heated by a high frequency induction coil 18.
  • the internal temperature of the graphite tube (reaction tube) 15 was such that the temperature could be arbitrarily controlled from 1,600 ° C. to 2,700 ° C., and the operation was performed at 2,500 ° C.
  • the SiO X that has become molten droplets (partially gasified) by the plasma flame 3 is entirely turned into SiO X gas by being blown into the high-frequency induction heating furnace 19, and is inert from the upper part of the induction induction furnace 19. It is sent to the outlet pipe 21 of the gas cooling device 20.
  • a compressed N 2 gas at room temperature was blown into the SiO X gas at 400 L / min from the ring-shaped nozzle 22 at the outlet of the outlet pipe 21 and rapidly cooled to 800 ° C.
  • the SiO X primarily cooled to 800 ° C. becomes a fine powder from the gas, and is further blown into the water-cooled cyclone 24.
  • the SiO X fine powder cooled by the water cooling cyclone 24 grows in particle size, adheres and accumulates on the side wall and the lower portion of the water cooling cyclone 24, and is collected in a hopper 26 provided at the lower portion of the water cooling cyclone 24.
  • the SiO X recovered powder collected at the bottom of the water-cooled cyclone 24 was sampled and subjected to particle size analysis and component analysis.
  • the SiO X recovered powder collected at the bottom of the water-cooled cyclone 24 was sampled and subjected to particle size analysis and component analysis.
  • the SiO X recovered powder collected at the bottom of the water-cooled cyclone 24 was sampled and subjected to particle size analysis and component analysis.
  • the analysis result of the SiO X recovered powder sample is X in both EDS analysis and XPS analysis.
  • the value was almost the same as the calculated X value at the raw material powder mixing ratio. It was also confirmed that the raw material Si component and SiO 2 component were almost lost even in the SiO X bonded state of the SiO X recovered powder sample, and Sub-oxide (Si 1+ , Si 2+ , Si 3+ ) was generated. .
  • the particle size distribution of the SiO X recovered powder sample is also suitable for application of the negative electrode active material of a lithium ion secondary battery having an average particle size D 50 : 18 ⁇ m to 33 ⁇ m (> 50 ⁇ m: 0% to 26%). It could be recovered as a fine powder of distribution.
  • the X value of SiO X can be optimally controlled according to the use, and the recovered SiO X is a powder having a particle size distribution suitable for application of the negative electrode active material of the lithium ion secondary battery.
  • the pulverization step for adjusting the particle size can be omitted, and the SiO X powder production cost can be greatly reduced.
  • Example 1 The raw material of the metal Si powder is put in a powder at a supply rate of 70 g / min into a plasma jet of a DC (direct current) plasma apparatus (manufactured by Nippon Yutech Co., Ltd .: SG-100 spray gun), and further SiO in the plasma flame 3
  • the fine powder having an average particle diameter D 50 of about 5 ⁇ m cannot be stably supplied by the powder supply device 14 of the plasma gun 2 because the powder is too fine.
  • the material supply was very unstable, and the recovered powder was composed of metal Si and SiO 2 despite being heated in the high-frequency induction heating furnace 19 after the plasma jet. There were many compositions, and SiO conversion reaction did not occur so much.
  • the metal Si powder is not granulated because it is not granulated, it is difficult for the powder to enter the center of the plasma flame 3, and the metal Si cannot be completely vaporized due to its high vaporization temperature. The gas phase reaction was difficult to occur.
  • Example 3 The operation was performed under the same conditions as in Example 1 except that heating in the high-frequency induction heating furnace 19 was not performed. Since the material is granulated, the material is melted in the plasma flame 3 because the raw material particle diameter is large. However, since the temperature of the plasma flame 3 rapidly decreases, the molten droplets of the mixed granulated powder 5 are solidified without being vaporized as they are. Moreover, since the particle diameter of the recovered powder is very large and no gas phase reaction is performed, a mixture of metal Si and SiO 2 in the form of particulate powder is large.
  • Comparative Example 4 A normal DC (direct current) plasma device (manufactured by Nippon Yutec Corp .: SG-100 spray gun) is used instead of a special nozzle in which the diameter of the nozzle 10 at the tip 2a of the plasma gun is increased in order to slow down the ejection speed of the plasma flame 3.
  • a normal DC (direct current) plasma apparatus that does not employ a special nozzle, the flying speed of molten droplets is very fast, and the residence time in the high-frequency induction heating furnace 19 is very short. Compared with Comparative Example 3, vaporization of the molten droplets was considerably carried out, but it was not sufficient.
  • Example 5 The same conditions as in Example 1 except that the high-temperature gas (about 1,700 ° C.) discharged from the high-frequency induction heating furnace 19 is discharged as it is into the heat insulating double tube 23 without performing the primary quenching with the compressed N 2 gas. Operated at. The high-temperature SiO X gas is released into the atmosphere of the water-cooled cyclone 24 through the heat insulating double tube 23, but the gas flow rate is slow and most of the gas is precipitated and solidified in the heat insulating double tube 23 or enters the cyclone. The particles also did not settle in the water cooled cyclone 24 and the yield was very bad.
  • the high-temperature gas about 1,700 ° C.

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CN116678217B (zh) * 2023-08-03 2023-10-13 四川士达贸易有限公司 一种锂电池负极材料石墨化工艺及设备
CN117001004A (zh) * 2023-09-28 2023-11-07 西安赛隆增材技术股份有限公司 一种微波等离子制粉装置及制粉方法
CN117001004B (zh) * 2023-09-28 2023-12-05 西安赛隆增材技术股份有限公司 一种微波等离子制粉装置及制粉方法

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